The size and strain effects on the Raman spectra of Ce1−xNdxO2−δ (0≤x≤0.25) nanopowders

Ultrafine Ce_1−xNd_xO_2−δ (x=0-0.25) powders were synthesized by self-propagating room temperature synthesis. Raman spectra were measured at room temperature in the 300-700 cm⁻¹ spectral range. The shift and asymmetric broadening of the Raman F_2g mode at about 454 cm⁻¹ in pure and doped ceria samples could be explained with combined size and inhomogenous strain effects. Increased concentration of O²⁻ vacancies with doping is followed by an appearance of new Raman feature at about 545 cm⁻¹.     

Vibrational properties of single-wall BC3 nanotubes

The phonon dispersions of single-wall BC₃ nanotubes with any chirality are calculated within a symmetry-based force constant model of the lattice dynamics. Based on the non-symmorphic symmetry group of the BC₃ tubes, the symmetries and number of the Raman- and infrared-active modes at Γ point of the one-dimensional Brillouin zone are given. The neighbor atom-atomic interaction force constants are recalculated by fitting them to the experimental phonon energy-dispersion curves of honeycomb BC₃ sheet. The frequencies of the optically active modes are presented as the function of diameters and chiralities for BC₃ tubes. The obtained phonon density-of-states spectra, phonon dispersion relations, and vibrational patterns of the zone-center phonons are presented and discussed in detail. The calculated frequencies of infrared-active modes are compared with the experimental values reported in the literature. The results provide comprehensive information about the vibrational properties of the BC₃ tubes and shed light on the interpretation of Raman scattering and infrared spectroscopies.     

Effect of H2 and O2 plasma etching treatment on the surface of diamond-like carbon thin film

In this study, we investigated the surface properties of diamond-like carbon (DLC) films for biomedical applications through plasma etching treatment using oxygen (O₂) and hydrogen (H₂) gas. The synthesis and post-plasma etching treatment of DLC films were carried out by 13.56 MHz RF plasma enhanced chemical vapor deposition (PECVD) system. In order to characterize the surface of DLC films, they were etched to a thickness of approximately 100 nm and were compared with an as-deposited DLC film. We obtained the optimum condition through power variation, at which the etching rate by H₂ and O₂ was 30 and 80 nm/min, respectively. The structural and chemical properties of these thin films after the plasma etching treatment were evaluated by Raman and Fourier transform infrared (FT-IR) spectroscopy. In the case of as-deposited and H₂ plasma etching-treated DLC film, the contact angle was 86.4° and 83.7°, respectively, whereas it was reduced to 35.5° in the etching-treated DLC film in O₂ plasma. The surface roughness of plasma etching-treated DLC with H₂ or O₂ was maintained smooth at 0.1 nm. These results indicated that the surface of the etching-treated DLC film in O₂ plasma was hydrophilic as well as smooth.     

Raman spectroscopy on single- and multi-walled nanotubes under high pressure

The pressure dependence of the high-energy Raman modes in single- and multi-walled carbon nanotubes was measured in the range 0–10 GPa. We found the pressure coefficient to be linear in both materials but 25% smaller in MWNT. Given that the curvature effects on vibrational properties of the rolled-up graphene sheets are small, we can explain this difference simply with elasticity theory. Received: 17 May 1999 / Accepted 18 May 1999 / Published online: 4 August 1999     

Photoluminescence enhancement and stabilisation of porous silicon passivated by iron

Iron is incorporated in porous silicon (PS) by impregnation method using Fe(NO₃)₃ aqueous solution. The presence of iron in PS matrix is shown from energy-dispersive X-ray (EDX) analysis and Fourier transform infrared (FTIR) measurements. The optical properties of PS and PS-doped iron are studied by photoluminescence (PL). The iron deposited in PS quenched the silicon dangling bonds then increased the PL intensity. The PL peak intensity of impregnated PS is seven times stronger than that in normal PS. Upon exposing iron-PS sample to ambient air, there is no significant change in peak position but the PL intensity increases during the first 3 weeks and then stabilises. The stability is attributed to passivation of the Si nanocrystallites by iron.     

The surface modification of nanoporous SiOx thin films with a monofunctional organosilane

The surfaces of nanostructured, porous SiO_x/Si (air-oxidized Si) and SiO_x thin films, deposited by excimer laser ablation in He and He + O₂ gas ambients, respectively, have been modified by the deposition of a monofunctional organosilane. They were characterized using photoacoustic Fourier-transform infrared (FTIR) X-ray photoelectron (XPS) spectroscopies, and field-emission scanning electron microscopy (FESEM). Photoacoustic FTIR analysis indicates that the organosilane has hydrolyzed to form a silanol, which has chemically reacted with SiO_x through its surface silanol (SiOH) group, to form siloxane (SiOSi) structures. An enhanced IR spectral signal is found, due to the expansion and contraction of both the pores of the solid and the gas within them.     

Plasmonic interactions between a metallic nanotube array and a thin metallic film

Using the finite difference time domain (FDTD) method, we numerically simulate the plasmonic interactions and the optical properties of a metallic nanotube array near a thin metallic film. We show that the energies and intensities of the plasmon resonances depend strongly on the aspect ratio (the ratio of the inner to outer radius) of the nanotube, the separation between the center of the nanotube and the upper surface of the metallic film and the thickness of the film. In the thin film limit, the high-energy localized tube-related plasmons can induce their images on both sides of the metallic film, so the degeneracy state splits into two modes. Based on the nature of the field distribution, we also show clearly the plasmon resonant characteristics that the electromagnetic fields decay away from the surface of the nanotubes and both sides of the metallic film.     

Charge and lattice dynamics of ordered state in La1/2Ca1/2MnO3: infrared reflection spectroscopy study

We report an infrared reflection spectroscopy study of La_1/2Ca_1/2MnO₃ over a broad frequency range and temperature interval which covers the transitions from the high temperature paramagnetic to ferromagnetic and, upon further cooling, to antiferromagnetic phase. The structural phase transition, accompanied by a ferromagnetic ordering at T_C=234 K, leads to enrichment of the phonon spectrum. A charge ordered antiferromagnetic insulating ground state develops below the Néel transition temperature T_N=163 K. This is evidenced by the formation of charge density waves and opening of a gap with the magnitude of 2Δ₀=(320±15) cm⁻¹ in the excitation spectrum. Several of the infrared active phonons are found to exhibit anomalous frequency softening. The experimental data suggest coexistence of ferromagnetic and antiferromangetic phases at low temperatures.     

Mott-type hopping conduction in the ordered and disordered phases of LiCoO2

The temperature dependence of dc resistance was observed in the range of for layered-rock-salt (hexagonal structure, ordered distribution between Li and Co) and modified-spinel (cubic, random distribution) phases of LiCoO₂. The results suggest Mott-type hopping conduction arising from the localized Co-3d electrons in the valence band. The densities of states (DOS) at the Fermi energy (E_F) estimated from the slope of the resistance curves were 2.0×10²⁰ and 5.5×10¹⁹ cm⁻³ eV⁻¹ for the ordered and disordered phases, respectively. The relatively low DOS at E_F in the disordered phase suggests that E_F approaches the edge of the valence band as a result of the narrowing of Co-t_2g bands due to the higher lattice symmetry in the disordered phase.     

Si layer transfer to InP substrate using low-temperature wafer bonding

Using a low-temperature wafer bonding process, InP substrates are bonded to silicon-on-insulator (SOI) substrates at 220 °C. A combination of oxygen plasma and chemical treatment results in a direct contact bonding at room temperature. After the bonding process at 220 °C for 45 min, removal of the Si handle substrate by sacrificial etching of the buried oxide layer in SOI, results in a thin membrane of Si robustly bonded to InP. The thin Si membrane bonded to InP shows uniformly bonded interface under high-resolution electron microscopy. Micro-Raman analysis has also been carried out to study the bonded interface. I-V characteristics of the bonded structures suggest that such bonding and layer transfer processes are suitable for device integration.     

Raman scattering and optical absorption studies of an orbital ordered Ca2RuO4

We have reported the Raman scattering and infrared absorption results on a t_2g orbital ordered Ca₂RuO₄. At 10 K, a strong and clear peak was observed in Raman scattering near 1360 cm⁻¹ with x′x′ geometry. In contrast to optic phonon modes, the peak does not show any frequency shift but rapidly decreases with increasing temperature. In addition, the peak is not observed in infrared absorption measurement. By comparing the previous Raman scattering results for several transition metal oxides, we have discussed the possible origins and ambiguities of the intriguing peak in Ca₂RuO₄.     

Room-temperature electrosynthesized ZnO thin film with strong (0 0 2) orientation and its optical properties

ZnO thin film with strong orientation (0 0 2) and smooth surface morphology was electrosynthesized on ITO-coated glass substrate at room temperature under pulsed voltage. Photoluminescence (PL) shows two obvious peaks: violet band and strong green band. The former is due to the free-excitonic transition and the latter is believed to arise from the single ionized oxygen vacancy (V_O⁺). Raman scattering reveals that the 580 cm⁻¹ mode and the shoulder peak mode at 550 cm⁻¹ originate from the N-related local vibration mode (LVM) and E₁ (LO) mode, respectively.     

Raman spectroscopy of pentyl‐functionalized carbon nanotubes

We present Raman scattering on carbon nanotubes functionalized with pentyl groups. Studies of the intermediate frequency region and the C–H bond stretching signal along with the D mode show evidence of the addition reaction by Raman spectroscopy. From the resonance profiles of the radial breathing mode (RBM) we assign the chiral indices of the tubes and study the influence of the functionalization on the transition energies, shift and intensity of the RBM signal. The largest effect we observe is on the Raman intensity of the radial breathing mode. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

     

Influence of hydrogenation on the structure and visible photoluminescence of germanium oxide thin films

Substoichiometric germanium oxide thin films were prepared by evaporation of GeO₂ powder. The as-deposited samples showed a luminescence band in the visible range. Hydrogen was used to passivate the dangling bond defects and therefore to determine the origin of photoluminescence in the germanium oxide films. Hydrogen was introduced in the films from an electron cyclotron resonance (ECR) plasma source during or after the evaporation. The films hydrogenated during evaporation contain little oxygen because of an etching mechanism. In the post-hydrogenated films, the oxygen content is higher. With the hydrogenation treatment, the oxygen dangling bonds are suppressed. It is proposed that the photoluminescence in the visible range is attributed to the structural defects.     

Investigation of SiO2/Si3N4 films prepared on sapphire by r.f. magnetron reactive sputtering

Sapphire is a desired material for infrared-transmitting windows and domes because of its excellent optical and mechanical properties. However, its thermal shock resistance is limited by loss of compressive strength along the c-axis of the crystal with increasing temperature. In this paper, double layer films of SiO₂/Si₃N₄ were prepared on sapphire (α-Al₂O₃) by radio frequency magnetron reactive sputtering in order to increase both transmission and high temperature mechanical performance of infrared windows of sapphire. Composition and structure of each layer of the films were analyzed by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), respectively. Surface morphology and roughness of coated and uncoated sapphire have been measured using a talysurf. Flexural strengths of sapphire sample uncoated and coated with SiO₂/Si₃N₄ have been studied by 3-point bending tests at different temperatures. The results show that SiO₂/Si₃N₄ films can improve the surface morphology and reduce the surface roughness of sapphire substrate. In addition, the designed SiO₂/Si₃N₄ films can increase the transmission of sapphire in mid-wave infrared and strengthen sapphire at high temperatures. Results for 3-point bending tests indicated that the SiO₂/Si₃N₄ films increased the flexural strength of c-axis sapphire by a factor of about 1.4 at 800 °C.     

Studies on surface modification of UHMWPE fibers via UV initiated grafting

In this research, the surface of ultra high molecular weight polyethylene (UHMWPE) fiber was modified by high energy ultraviolet (UV) initiated grafting reactions and acrylamide groups were grafted onto UHMWPE chains. The initiating and grafting mechanism of the reactions was studied. Some important factors influencing the grafting effect, e.g. crystallinity of UHMWPE fiber, concentration of the initiating reagent, grafting time and the concentration of grafting monomer (acrylamide) were discussed. Fourier transform infrared (FTIR) was used to manifest the mechanism of the grafting reaction. Scanning electron microscopy (SEM) was used to show the morphology changing of the fiber surface. Single fiber pull-out strength and ILSS tests of the composite showed that acrylamide grafted onto the surface of the fiber could improve the interfacial adhesion between treated fibers and matrices.     

Effect of dc-Joule-heating thermal processing on magnetoimpedance of Fe72Al5Ga2P11C6B4 amorphous alloy

The effect of multistep dc-Joule-heating thermal processing on magnetoimpedance (MI) of Fe₇₂Al₅Ga₂P₁₁C₆B₄ ribbons is presented. After material optimization significant increase of MI response up to value ΔZ/Z≈55% as well as sensitivity of about 6%/kA/m (for H?3–4 kA/m), were recorded in still amorphous samples at driving frequencies 2–3 MHz. On-line and post-annealing electrical resistivity together with Mössbauer spectra analysis and frequency dependence of the penetration depth were used for characterization of MI improvement.     

Effect of ZnS shell on the Raman spectra from CdSe nanorods

We investigated the influence of an epitaxially grown ZnS shell on the phonon spectra of CdSe nanorods of different sizes. The CdSe related Raman peaks shift with addition of a ZnS shell. The longitudinal optical phonon shifts slightly due to strain and the low‐energy shoulder shifts stronger, which can be explained within a model for surface optical phonons. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman scattering characterization of vertical aligned 1D IrO2 nanocrystals grown on single crystal oxide substrates

Raman scattering (RS) has been used as a technique for characterization of IrO₂ one dimensional (1D) nanocrystals (NCs) deposited on sapphire(100) and LiNbO₃(100) substrates under various conditions. The IrO₂ NCs were grown via metalorganic chemical vapor deposition method using (MeCp)(COD)Ir as the precursor and reactive magnetron sputtering using Ir metal target. The red-shifts and asymmetric broadening of the Raman lineshape for the NCs were analyzed by a modified spatial correlation (MSC) model, which includes the factor of stress induced shift. The proposed MSC model showed that the effects of stress and nanometric size can be separated in analyzing the observed Raman features. The usefulness of the experimental RS together with the MSC model analysis as a residual stress and structural characterization technique for 1D NCs has been demonstrated.